Bulk catalysts based on chromium and on nickel for the gas-phase fluorination of halogenated hydrocarbons

ABSTRACT

Catalysts which are useful in the fluorination of halogenated hydrocarbons by HF in the gas phase are obtained by simple impregnation of a bulk chromium oxide with a solution of a nickel derivative, the chromium oxide used exhibiting a BET specific surface of greater than 150 m 2 /g and a pore volume of greater than 0.15 ml/g.

DESCRIPTION

[0001] The present invention relates to the field of the fluorination ofhalogenated hydrocarbons and more particularly to the preparation ofbulk catalysts based on chromium and on nickel which can be used forthis purpose.

[0002] One of the various access routes to hydroalkanes, which aresubstitutes for CFCs (ChloroFluoroCarbons), is gas-phase fluorinationwith HF. For this, many catalysts are described in the literature and agood number of them are based on chromium. The change from CFCs to thesubstitutes has led to research into the catalysts in order to improvetheir performances, both from the viewpoint of activity and ofselectivity.

[0003] First of all, studies have been carried out in order to improvethe performances of chromium-based catalysts. Thus, Patent ApplicationEP 514,932 claims, as fluorination catalyst, a chromium oxide with ahigh specific surface which, according to the authors, has a highactivity and a long lifetime.

[0004] In the same way, work has been carried out in order to modify theperformances of chromium-based catalysts by addition of doping agents orof cocatalysts. Thus, as regards mixed Ni—Cr catalysts, Patent FR2,669,022 claims the synthesis of F134a (1,1,1,2-tetrafluoroethane) bygas-phase fluorination of F133a (1-chloro-2,2,2-trifluoroethane) over acatalyst based on derivatives of nickel and of chromium which aresupported on more or less fluorinated aluminas, or even on aluminiumfluoride. The presence of the support contributes certaincharacteristics to the catalyst, in particular a degree of strength. Onthe other hand, there is a risk, with the small amounts of activematerials, of limiting the catalytic activity, or even the lifetime ofthe catalyst; in addition, the low contents of non-precious metals donot facilitate a profitable recovery of the spent catalysts.

[0005] Patent EP 546,883 describes the preparation of bulk catalystsbased on chromium and on nickel by the sol-gel method in several stages,the first consisting in forming a mixed sol of chromium III and nickelII hydroxides. This technique, which starts with a mixture of theprecursors of the chromium and of the nickel, is relatively lengthy andexpensive to implement.

[0006] In Patent Application WO 93/25507, the preparation of catalystsbased on chromium and on at least one derivative of a transition metalchosen from nickel, platinum and palladium is carried in various ways:impregnation of a support, coprecipitation, impregnation of a chromiumderivative, and the like. No characteristic of the catalyst or of thesupport is provided in this document.

[0007] It has now been found that a mixed Ni—Cr catalyst which isparticularly effective in the gas-phase fluorination by HF of saturatedor olefinic halogenated hydrocarbons can be obtained by simpleimpregnation of a bulk chromium oxide, with a large specific surface andwith a high pore volume, with a solution of a nickel derivative.

[0008] The subject of the invention is thus bulk catalysts based onchromium and on nickel which are obtained by impregnation of anamorphous chromium III oxide with a solution of a nickel derivative,characterized in that the bulk chromium oxide used exhibits a BETspecific surface of greater than 150 m²/g, preferably of greater than180 m²/g, and a pore volume (defined as the volume of the pores with aradius of less than 7.5 μm) of greater than 0.15 ml/g, preferably ofgreater than 0.18 ml/g.

[0009] A chromium III oxide with a BET specific surface greater than 150m²/g can be synthesized by the various techniques known to the personskilled in the art. Mention may be made, as non-limiting example, of thecalcination of a chromium III hydroxide precipitate, the formation of achromium III hydroxide gel, followed by the calcination thereof, thereduction of chromium VI by an alcohol or another reducing agent, or thethermal decomposition of an oxidized derivative of chromium, such asCrO₃ and (NH₄)₂Cr₂O₇. It is preferable to use a chromium oxide obtainedby calcination of a chromium III hydroxide or by reduction of chromiumVI oxide. Commercial chromium III oxides may be suitable, provided thatthey have a suitable specific surface and a suitable porosity.

[0010] Chromium III oxide can be provided in various forms (pellets,extrudates, balls, and the like). The form used very clearly establishesthe form of the final catalyst; it must therefore not be detrimentallyaffected by the impregnation stage. To achieve this, various additives(graphite, crystalline Cr₂O₃, and the like) can be added during theshaping operation, in order to improve the strength of the chromiumparticles.

[0011] Chromium III oxide is impregnated by means of an aqueous oralcoholic solution of a nickel precursor which can be a nickel II oxide,hydroxide, halide, oxyhalide, nitrate, sulphate or other compound whichis soluble in aqueous or alcoholic medium. The preferred compound isnickel chloride.

[0012] The Ni/Cr atomic ratio in the final catalyst can vary between0.01 and 1, preferably between 0.02 and 0.6. An atomic ratio of between0.02 and 0.4 is particularly advantageous. The impregnation of thechromium oxide can be carried out before the catalyst is shaped(impregnation of Cr₂O₃ powder) or on chromium III oxide which hasalready been shaped (balls, pellets, extrudates, and the like). Thelatter technique is preferred when the form of the catalyst is notdetrimentally affected by the impregnation stage. The impregnation canbe carried out according to the various techniques known to the personskilled in the art (immersion, impregnation with a volume adjusted tothe porosity of the catalyst, and the like). Impregnation adjusted tothe pore volume of the catalyst is the preferred technique. Theimpregnation solution can be an aqueous solution or an alcoholicsolution. When there is no solubility problem, the aqueous solution ispreferred; the exothermicity due to the reduction by the alcohol of thesurface chromium VI (always present at a low content in Cr₂O₃) is thusavoided.

[0013] In order to optimize the activity of the catalyst, it isadvisable to subject it to a pretreatment with HF in the absence oforganic compounds. As chromium III oxide and the nickel derivativesbecome fluorinated in the presence of HF, it is necessary to carry outthis fluorination while controlling the exothermicity of the reaction,in order to prevent the catalyst from deteriorating (crystallization,deterioration of the balls, pellets or extrudates, and the like). Atypical pretreatment (or activation) of the catalyst first comprises adrying stage under an inert gas (nitrogen, helium, or the like) or airat a temperature of between 100 and 350° C., followed by a stage ofactivation by HF. To control the exothermicity, the HF is, on the onehand, introduced at low temperature (150-200° C.) and, on the otherhand, it is diluted in air or, preferably, in an inert gas. After the“exothermicity waves” due to the adsorption of HF on the catalyst havepassed, the temperature is gradually increased, in order to reach350-380° C. and to observe a stationary phase at this temperature. Whenthe strength of the catalyst allows it, the latter can be activated as astirred or fluidized bed; control of exothermicity is thus easier. Inorder to avoid any deterioration in the catalyst, it is recommended thata temperature of 400° C. should not be exceeded.

[0014] Another subject of the invention is the use of these bulkcatalysts for the catalytic fluorination of saturated or olefinichalogenated hydrocarbons by HF in the gas phase.

[0015] The halogenated hydrocarbons capable of resulting in HCFCs(HydroChloroFluoroCarbons) or in HFCs (HydroFluoroCarbons) by gas-phasefluorination are compounds containing one or more carbon atoms whichresult in final products, or even in synthetic intermediates, containingone or more hydrogen atoms. Mention may be made, as non-limitingexamples, in this category, of the following compounds: CH₂Cl₂, CH₂ClF,CHCl₃, CCl₂═CHCl, CCl₂═CCl₂, CH₂Cl—CF₃, CHCl₂—CF₃, CHClF—CF₃, CH₃—CCl₃,CH₃—CCl₂F, CH₃—CClF₂, C₃F₆, CCl₃—CH₂—CHCl₂, CF₃—CH═CHCl, CF₃—CH₂—CHClF,CH₃—CCl₂—CH₃, CCl₃—CF₂—CHCl₂, CCl₃—CF₂—CH₂Cl, CCl₃—CF₂—CH₃,CHCl₂—CHCl—CH₃, CH₂Cl—CHCl—CH₃, and the like.

[0016] The fluorination temperature depends on the starting halogenatedhydrocarbon and, very clearly, on the desired reaction products. It isgenerally between 50 and 500° C. but it is often preferable to carry outthe fluorination at a temperature of between 100 and 450° C. and moreparticularly between 120 and 400° C.

[0017] The contact time also depends on the starting material and thedesired products. It is generally between 3 and 100 seconds. A goodcompromise between a high degree of conversion and a high productivityvery often lays down a contact time of less than 30 seconds.

[0018] The molar ratio: HF/organic reactant(s) is also related to thenature of the starting material and depends, inter alia, on thestoichiometry of the reaction. In the majority of cases, it can varybetween 1/1 and 30/1. However, in order to obtain high productivities,it is advantageously less than 20.

[0019] The working pressure is not critical but is generally between0.08 and 2 MPa absolute and, preferably, between 0.1 and 1.5 MPaabsolute.

[0020] The catalysts can operate as a stationary bed but also, when theyallow this, as a fluid or stirred bed.

[0021] When the fluorination reaction results in fouling of the catalyst(formation of “coke”), it is possible to carry out the fluorination bycontinuously injecting an oxidizing agent (air, oxygen, or the like).When the catalyst is deactivated by coking, it is also possible toregenerate by a treatment with air or with oxygen or by a Cl₂/HFmixture, at a temperature of between 250 and 400° C.

[0022] The following examples illustrate the invention without limitingit.

PREPARATION OF THE CATALYSTS EXAMPLE 1 Catalyst A

[0023] 100 ml (139 g) of a commercial chromium III oxide in the form ofpellets exhibiting the following characteristics: BET specific surface(m²/g) 223 Pore volume (r < 7.5 μM) 0.272 ml/g graphite (pelletingbinder) 4.1 weight %

[0024] are impregnated at room temperature and atmospheric pressure witha nickel chloride solution composed of 22.6 g of NiCl₂.6H₂O in 20 ml ofwater.

[0025] At the end of impregnation, all the solution is absorbed by thecatalyst. The latter is then dried at room temperature and atatmospheric temperature.

[0026] This impregnated catalyst is then dried under nitrogen at 200° C.for 18 hours and then a portion (70 ml) is activated with a nitrogen/HFmixture, the temperature being controlled so as not to exceed anexothermicity of 30° C. with respect to the set temperature. The mixtureis gradually enriched in HF and the temperature gradually increased toreach 380° C. under pure HF (1 mol/h of HF). Finally, the catalyst ispretreated with pure HF under these operating conditions for 18 hours.

[0027] The catalyst, thus impregnated, dried and activated, contains3.5% by mass of nickel.

EXAMPLE 2 Catalyst B

[0028] 100 ml of the chromium III oxide described in Example 1 areimmersed at room temperature in an aqueous nickel chloride solutionprepared by dissolving 75 g of NiCl₂.6H₂O in 35 ml of water. Thecatalyst is then dried and then activated according to the procedure ofExample 1.

[0029] The catalyst, thus impregnated, dried and activated, contains4.2% by mass of nickel.

EXAMPLE 3 Catalyst C

[0030] This catalyst is prepared, dried and activated according to theprocedure of Example 1, except that the impregnation solution iscomposed of 34 g of NiCl₂.6H₂O and 18 ml of water.

[0031] After drying and activation, the catalyst, thus impregnated,contains 5.1% by mass of nickel.

COMPARATIVE EXAMPLE 4 Nickel-free Catalyst D

[0032] The chromium III oxide described in Example 1 is used directlywithout being subjected to impregnation by nickel. Before thefluorination test, the catalyst is subjected to an N₂/HF pretreatmentcomparable to that described in Example 1.

COMPARATIVE EXAMPLE 5 Catalyst E Prepared From a Chromium Oxide WhichDoes Not Observe the Specific Surface and Porosity Criteria

[0033] 100 ml of a commercial chromium oxide in the powder form,exhibiting the following characteristics: BET specific surface (m²/g) 66Pore volume (r < 7.5 μm) 0.14 ml/g

[0034] are impregnated by immersion in an aqueous nickel chloridesolution consisting of 75 g of NiCl₂.6H₂O and 35 ml of water. Thecatalyst is then dried and then activated according to the procedure ofExample 1.

[0035] After drying and activation, the catalyst, thus impregnated,contains 3.6% by mass of nickel.

Fluorination Examples

[0036] The catalysts described in Examples 1 to 5 were used in thegas-phase fluorination of perchloroethylene (Examples 6 to 11) and of1-chloro-2,2,2-trifluoroethane (Examples 12 and 13).

[0037] The operating conditions and the results obtained are combined inthe following Tables I and II, where the abbreviations have thefollowing meanings: F114 + F114a dichlorotetrafluoroethanes F115chloropentafluoroethane F122 1,1-difluoro-1,2,2-trichloroethane F1231,1-dichloro-2,2,2-trifluoroethane F123a1,2-dichloro-1,1,2,-trifluoroethane F1241-chloro-1,2,2,2-tetrafluoroethane F124a1-chloro-1,1,2,2-tetrafluoroethane F125 pentafluoroethane F143a1,1,1-trifluoroethane F1111 fluorotrichloroethylene F11221-chloro-2,2-difluoroethylene

[0038] The examples 6 to 9, carried out with the catalysts A, B and Caccording to the invention, show that these catalysts, which are easy toprepare (simple impregnation of a commercial chromium oxide), are verygood fluorination catalysts; moreover, the recovery of these spentcatalysts is profitable on account of the chromium contents.

[0039] The tests of Example 10, which are carried out with the catalystD, reflect, in comparison with the results obtained with the catalystsA, B and C, the beneficial effect of nickel.

[0040] Finally, the tests of Example 11, which are carried out with thecatalyst E, show that a catalyst prepared with a chromium oxide whichdoes not observe the specific surface and pore volume criteria definedin the present invention gives markedly poorer fluorination results.TABLE I Fluorination of perchoroethylene 10, 11, EXAMPLE 6 7 8 9Comparative Comparative OPERATING CONDITIONS Catalyst A A A A B C D D EE Temperature (° C.) 300 350 280 280 280 300 350 300 300 350 Molarratio: HF/C₂Cl₄ 7.1 7.1 7.2 6.8 6.9 6.9 6.1 7.0 7.3 7.1 Molar ratio:Oxygen/C₂Cl₄ 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Pressure(MPa) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Contact time (seconds) 5.24.9 5.4 5.4 5.5 5.3 5.5 5.1 5.3 5.4 Age of the catalyst (hours) 24 48 48448 44 24 24 48 24 48 RESULTS Overall degree of conversion 72.3 82.666.7 62.6 65.2 69.3 91.2 72.8 53.8 60.6 of C₂Cl₄ (%) Selectivity (molar%) for: F125 22.2 49.8 10.3 8.9 9.1 19.8 25.0 15.3 4.3 7.4 F124 32.316.7 31.3 34.6 29.0 32.5 11.6 32.3 23.1 30.6 F124a 1.5 0.7 1.4 1.9 1.51.5 0.2 1.5 1.4 1.7 F123 30.5 13.5 42.0 37.7 44.5 32.3 22.0 36.1 47.237.4 F123a 1.9 0.5 2.8 2.9 2.4 1.9 0.1 1.7 4.6 1.9 F122 3 0.7 5.4 5.56.2 3.6 0. 2.5 10 5.6 F133a 0.6 4.8 0.4 0.2 0.3 0.6 11.1 2.5 0.4 3.5F155 0.5 5.3 0.2 0.1 0.1 0.7 21.3 2.1 0.5 4.8 F114 + F114a 2.2 3.1 1.81.2 1.6 2.1 7.0 3.0 1.6 3.1 F1111 4.6 4.1 4.2 6.5 5.0 4.9 0.9 2.9 6.53.1 Others 0.7 0.8 0.2 0.5 0.3 0.1 0.6 0.1 0.4 0.9

[0041] TABLE II Fluorination of F133a 12, EXAMPLE Comparative 13OPERATING CONDITIONS Catalyst D A Temperature (° C.) 350 350 Pressure(MPa) 1.5 1.5 Molar ratio: HF/F133a 2.0 2.0 Molar ratio: Oxygen/F133a0.01 0.01 Contact time (seconds) 21.8 22.1 Age of the catalyst (hours)23 24 RESULTS Overall degree of con- 15.5 15.4 version of F133a (%)Selectivity (molar %) for: F134a 90.8 96.1 F1122 0.2 0.1 F123 1.2 0.6F124 1.3 0.8 F125 0.7 0.4 F143a 0.4 0.1 Others (CO, CO₂, 5.4 1.9 CHF₃,and the like)

[0042] Although the invention has been described in conjunction withspecific embodiments, it is evident that many alternatives andvariations will be apparent to those skilled in the art in light of theforegoing description. Accordingly, the invention is intended to embraceall of the alternatives and variations that fall within the spirit andscope of the appended claims. The above references are herebyincorporated by reference.

1. Bulk catalysts based on chromium and on nickel which are obtained byimpregnation of an amorphous chromium III oxide with a solution of anickel derivative, characterized in that the chromium oxide usedexhibits a BET specific surface of greater than 150 m²/g and a porevolume of greater than 0.15 ml/g.
 2. Catalysts according to claim 1,which are obtained from a chromium oxide having a BET specific surfaceof greater than 180 m²/g.
 3. Catalysts according to claim 1 or 2, whichare obtained from a chromium oxide exhibiting a pore volume of greaterthan 0.18 ml/g.
 4. Catalysts according to one of claims 1 to 3, in whichthe chromium oxide used originates from the calcination of a chromiumIII hydroxide precipitate or from the reduction of chromium VI oxide. 5.Catalysts according to one of claims 1 to 4, in which the nickelderivative is a nickel II oxide, hydroxide, halide, oxyhalide, nitrateor sulphate, preferably nickel chloride.
 6. Catalysts according to oneof claims 1 to 5, in which the Ni/Cr atomic ratio is between 0.01 and 1,preferably between 0.02 and 0.6 and more particularly between 0.02 and0.4.
 7. Catalysts according to one of claims 1 to 6, which are obtainedby means of an aqueous or alcoholic solution of a nickel derivative. 8.Process for the catalytic fluorination of saturated or olefinichalogenated hydrocarbons by HF in the gas phase, characterized in that acatalyst according to one of claims 1 to 7 is used.
 9. Process accordingto claim 8, in which, before it is used, the catalyst is dried under aninert gas or under air at a temperature of between 100 and 350° C. andthen activated with HF.
 10. Process according to claim 9, in which theHF is first introduced diluted in air or, preferably, in an inert gas ata temperature ranging from 150 to 200° C. and then pure at a temperatureof less than 400° C., preferably of between 350 and 380° C.
 11. Processaccording to one of claims 8 to 10, in which the fluorinationtemperature is between 50 and 500° C., preferably between 100 and 450°C. and more particularly between 120 and 400° C.
 12. Process accordingto one of claims 8 to 11, in which the contact time is between 3 and 100seconds, preferably less than 30 seconds.
 13. Process according to oneof claims 8 to 12, in which the molar ratio: HF/halogenatedhydrocarbon(s) is between 1/1 and 30/1, preferably less than 20/1. 14.Process according to one of claims 8 to 13, in which the fluorination iscarried out at an absolute pressure of between 0.08 and 2 MPa,preferably between 0.1. and 1.5 MPa.
 15. Process according to one ofclaims 8 to 14, in which the fluorination is carried out in the presentof an oxidizing agent, preferably oxygen or air.
 16. Process accordingto one of claims 8 to 15, in which the catalyst, deactived by coking, isregenerated by treatment with air or with oxygen or by a Cl₂/HF mixture,at a temperature of between 250 and 400° C.
 17. Process according to oneof claims 8 to 16, in which the halogenated hydrocarbon isperchloroethylene or 1-chloro-2,2,2-trifluoroethane.